Method of hydrolysis



I I filtered, washed and calcined.

solution of a composition of about Patented Mar. 14, 1944 UNITED "STATES PATENT osrlc's- 2.844.265

Walter W. l'leehner, Metuchen; and Joseph M.

Jum s, m Orange, N. 1., alaignors to Na-. tional Lead Company, New York, N. Y., a corporation of New Jersey No Drawing. 'plicatlon December 24, 1940, I

s e'i-mno. 371,588

The present invention relates to the manufacture of pigments especially titanium dioxide pigments and has particular reference to the hydrolysis step in the process of manufacturing said pigments. 4 F

Among the objects of the present invention is the production of a pigment-forming hydrous titanium oxide'having improved filtering and washing characteristics, as a consequence of which it is possible to produce titanium dioxide pigments more 'efiiclently and economically.

Other objects and advantages will become appar- V eat as the description of the invention proceeds.

The usual process for manufacturing titanium dioxide pigments is now well known. Broadlying the solution to the desired titanium content,

and thermally hydrolyzing the titanium sulfate solution to precipitate hydrous titanium oxide which is separated from the mother liquor,

We have now unexpectedly found a method of hydrolysis whereby the precipitated hydrous titanium oxide is rendered more easily filterable and washable without in any way impairing, and indeed, in some instances improving the pigmentary properties of the ensuing titanium dioxide pigment.

Our novel method is adaptable to commonly used hydrolysis processes employing titanium sulfate solutions and also is particularly useful in such processes where, for the purpose of improving the pigmentary properties of the calcined precipitate, antimony is introduced at pre cipitation instead of at calcination.

According to the practice of our invention, a portion only of the sulfate solution is subjected to an incomplete thermal hydrolysis, whereupon the remaining portion of the total sulfate solution is added, and the whole then thermally brought to assubstantially complete hydrolysis v of the titanium alues.

In one preferred procedure of our invention a 5 Claims. ores-202 added in about minutes under constant agitation to a volume of water or dilu acid heated to'90-l00 C. and equal to about per cent of the total volume of solution-water mixture. The solution-water mixture is then. brought to a boil, boiled for about one-half hour to about two hours while the stirring is continued, during which time the major rutrt of the titanium values in solution was precipitated. At this point the smaller portion of solution which was set aside at the beginning of the lwdrolysis is added and the whole boiled for about three to four hours under constant agitation at which time the hydrolysis is brought to completion.

It was found that the deliquoring and washing rates'of the precipitate obtained by this novel procedure were substantially improved over those obtained when the total amount of solution was at once subjected to. hydrolysis. It. was also found that the pigment properties of the finished titanium dioxide pigment were in no way imsulfate solution from which it is precipitated topaired.

We have further found that our method'is con-. venient when, for the purpose of improving the pigmentary properties of the final product, antimony is introduced into the precipitate via the gether with the titanium values. It was found that if antimony trioxide equal to about 2% to tn the total T10: in solution, was dissolved therein prior to the hydrolysis that the final precipi-.

t'ate could be deliquored and washed only with the greatest of difiiculty. when, however, the

antimony trioxide was dissolved in the smallerrior to the filtering and washing rate of precipitates obtained when noantimony was present in solution.

When the hydrolysis is carried out in the above about 5%, but preferably about 1%, calculated manner according to the practice of our invention, the yields obtainable of precipitated hydrous titanium oxide are excellent, being about 96.5

per cent of the titanium values in solution. 'Moreover, our novel method of hydrolysis makes it possible to obtain hydrous titanium oxide precipitates having greatly improved filtering and washingcharacteristics as compared with prior art precipitates. This fact is clearly shown from portion equal to about 10 per cent of an ilmenite is set aside, the other main portion, equal-to v methods.

about per cent is heated to 90-100' c. and then Before proceeding further it is desirable for the the figures hereinafter set forth wherein the filtering and washing rates of hydrous titanium oxide hydrolyzed according to thepresen't invention are compared with the filtering and washing rates of an equal quantity .of hydrous titanium oxide precipitated byusual prior. art hydrolysis in minutes and fractions thereof which is required for 500 cc. 'of the final precipitation at 85 C. to be deliquored, i. e., sucked dry under a vacuum of about 28" on a 19 cm. Buchner funnel using 'two wetted No. 5; 18.5 cm. Whatman filter papers without permitting the filter cake to crack.

The washing rate is the time expressed in which is dissolved antimony trioxide, 59.0.. in

an amount equal to one-per cent calculated on the T: of the total solution.

A. In one liter of stock ilmenite solution (see 5 Example 1) of 250 g. p. l. TiOz were dissolved 2.5 grams of SbzOa. The precipitation procedure was otherwise the same as that described under Example 1.

The deliquoring and washing rates of the final precipitate were such as to be incapable of "economical filtration.

B. When the 2.5 grams of antimony trioxide were dissolved in 100 cc. of the solution, Le, 10 per cent, instead of in the entire one liter as This experiment represents a regular method of hydrolysis of the prior art and serves as a standard for comparison.

A. Oneliter of an ilmenite solution of the composition a G. p. 1.. T102 (1- -2 g. p. l. in the trivalent form) 250 Fe 180 H250 500 heated to 96' C. was added uniformly to 250 cc.

of water of 91 0. over a period of .18 minutes more or less constant value during the hydrolysis nearly boiling water was periodically added tothe precipitation.

At the end of-a total boiling time of about six (6) hours, 500 cc. of the finished precipitation .were deliquored and washed according to the technique already described whereby the rate of .deliquoring and rate of washing were determined.

. B. When this experiment was repeated using 90 per cent of the solution. and then adding to the hydrolysis the remaining 10 per cent accordin: to the present invention, the rates of deliquor- 7 were substantially improved.

Exams: 2 This experiment represents a.regular method ins and washing minutes or fractions thereof required for 500 cc. under (A) above, and wasadded to the-hydrolysis of water at room temperature to pass through the of the other 900 cc. solution at a later stage, deliquored precipitate obtained above. according to our novel method, but otherwise The total washing time, i. e., the time required carrying out the experiment. according to the to wash the precipitate "free 0! iron is recorded procedure of Example 1-3, the rate of deliquoring in some'cases. was increased about three times over 2-A, and Although we already have described our invenwas even superior to the rate of deliquoring and tion in sufllcient detail to enable those skilled in washing obtained in Example l- -B where no antithe art tcwork our novel process we shall now mony was present. proceed to illustrate by the aid of actual exam- The following table clearly and succinctly illus- Dles the advantages embodied in the presentdn- 25, tratestheimproved results of-the present invenvention. tion. a

Tobie 1 r Washing g? Precipitation data Antimony addition Pa m? 7 7 Rate Time l-A precipitation"... Non 5 12" 13' 47" 1-D l Gigi efiglution added at an advanced stage 0! hy- .-.--do 4 4 1 2-a...- sbioil iiaoivodiniun volume ciilmenits solution. 1. on total 'ri0,-. 10' an" as 10" 70' 0" 2-D 10% 0! solution, in which was dissolved the Sbi0i, l. a ontotal T101111 3 67" 7' 36 18 i5 added at an advanced stage oi hydrolysis. I 10% of solution.

Exmu 1 i It is evident from Table 1 that the deliquor-.

ing and washing ratg of the precipitates were noticeablydmproved when 10 per cent of the solution, according to the practice of our invention were added to the hydrolysis at an advanced stage. The improvement in filtering and washing characteristics is particularly marked in those cases where antimony is dissolved in the solution. When antimony is present in the solution at the start of a regular precipitation the slow 60 rate of deliquoring and washing of the precipitate'becomes prohibitive for an operation, whereas, when the antimony is dissolved in the 10' per cent of solution and added-to-the hydrolysis at a later time, the filtering characteristics are enormously improved.

It should be clearly understood that our improved process is applicable to the hydrolysis of titanium sulfate solutions of a wide range of concentrationsand great variations-o! composition oil in respect'to the ratio of TiOatFeSOuHaSOs.

Our process is equally as useful in other hydrolysis than that used herein for illustrative pm H I Accordingly. we do not wish to limit our invention in any way to a solution of pich ccncentration and composition as herein has been employed to illustrate our novel process, nor do we limit our invention to the particular processof hY-r o drolysis which is used herein to demonstrate the advantages of the invention.

Likewise, the proportion of unhydrolyzed solution to partly hydrolysed solution in our process isnotlimitedtotheratiousedintheexample,

of hydrolysis of the prior art using a solution in 7; namely, a ratio of 10:90, but we may operate the It will thus be seen that by our novel method 3. A process for hydrolyzing a titanium salt solution which comprises dividing the said titanium salt solution into a major portion of about 90% oi the solution and a minor portion of about 10% or the solution, subjecting the said major portion of the solution to a thermal hydrolysis, without further addition or titanium salt solution,

' until the titaniumvalues of said major portion are partly precipitated, mixing the minor portion mixture until the titanium values contained of hydrolysis it is possible to manuiacture titanium dioxide pigments more economically by virtue oi the savings eflfected in time 01' washing and filtering and power consumption of the filterins ap a us. Y

F It is to be understood that the present invene tion is applicable not only to titanium dioxide pignientabut also to its composites and other pigments which are prepared by processes involving a hydrolytic step similar to that employed in producing titanium dioxide pigments. I

We claim: a

1. A process for hydrolyzlng a-titanium salt solution which comprises dividing the said titanium salt solution into a major portion and a minor portion, hydrolyzing the said major portion,- without further addition of titanium salt solution, until the titanium values of said major portion are partly precipitated-mixing the minor portion oi. said titanium salt solution with the partly hydrolyzed major portion and then hydrolyzing the mixture .until /the titanium values cohtained vtherein are substantially completely precipitated.

3s A process forhydrolyzing a titanium salt solution which comprises dividing the said titanium salt solution into a major portion and a minor portion, subjecting the said major portion or the solution to a thermal hydrolysis, without further 01' said titanium salt solution with the partly hydrolyzed major portion and then hydrolyzing the therein are substantially completely precipitated.

4. A process for hydrolyzing a titanium salt solution which'comprises dividing the said titanium salt solution into. a major portion and a minor portion, subjecting the said major portion or the solution toa thermal hydrolysis, without further addition oi. titanium. salt solution, until the titanium values oisaid major portion are,

partly precipitated, dissolving a small amount of an antimony compound in the minor unhydrolyzed portion 0! the solution, then mixing the said minor portion with the partly major portion and hydrolyzing the mixture until the titanium values contained therein are substantially completely precipitated.

5. A. process for hydrolyzing a titanium salt so- I lution which comprises dividing the'said titanium addition oi titanium salt solution, until the titanium values of asid major portion are partly preeipitated,mixing the minor portion oi. said titanium salt solution with the partly hydrolysed major-portionandthenhydrolyaingthemixture untiltbe titanimn values contained therein are substantially completely precipitated.

salt solution into a major portion of about 90% of the solution and a minor portion of about 10% or the solution, dissolving in the.said mino portion a small amount of an antimony compound,

subjecting the junior portion of the solution to a thermal hydrolysis, without further addition or titanium salt solution, until the titanium valuesof said major portion are partly precipitated, thenmixing the unhydrolyzed minor portion of the titanium salt solution in which. the antimony compound has been dissolved with the'partly l vdrolyzed major portion of the solution and bydrolyzing the mixture until the titanium values contained therein are substantially completely Precipitated.

' JOSEPH M. JARMUS. 

